CN105273166A - Preparation method of biological-based epoxy resin - Google Patents
Preparation method of biological-based epoxy resin Download PDFInfo
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- CN105273166A CN105273166A CN201410353485.2A CN201410353485A CN105273166A CN 105273166 A CN105273166 A CN 105273166A CN 201410353485 A CN201410353485 A CN 201410353485A CN 105273166 A CN105273166 A CN 105273166A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 35
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 23
- -1 poly(lactic acid) Polymers 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000003808 methanol extraction Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 244000061456 Solanum tuberosum Species 0.000 abstract description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 abstract description 3
- 240000008042 Zea mays Species 0.000 abstract description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 abstract description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 235000005822 corn Nutrition 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000004626 polylactic acid Substances 0.000 abstract 5
- 125000003700 epoxy group Chemical group 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920006025 bioresin Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention relates to a preparation method of a biological-based epoxy resin, maleic anhydride is used for end group modification of low-molecular-weight polylactic acid to obtain polylactic acid having two carboxyl-terminated ends. Under conditions of a zinc powder as a catalyst and DMSO as a solvent, polylactic acid is modified with epoxypropyl methacrylate, and two ends of a polylactic acid molecular chain are introduced with epoxy groups; and finally, an appropriate curing agent is added to initiate ring opening of the epoxy groups, a three-dimensional reticular structure is formed through crosslinking, and curing is carried out. The process is simple, polylactic acid is derived from corn, potato and other crops, raw material sources are wide, the consumption of high-molecular material on petroleum resources is facilitated to be reduced, and the emissions of CO2 is facilitated to be reduced; the prepared epoxy resin has lower viscosity and good adhesion property, can be used as substrates of adhesives, coatings and composite materials, and is suitable for molding process of various composite materials. Therefore, the epoxy resin has relatively broad application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of epoxy resin, especially a kind of preparation method of bio-based epoxy resin.
Background technology
Epoxy resin is containing two or more epoxide group, with aliphatics or aromatic series for skeleton, and reacts the high-molecular oligomers thing generating thermoset products by epoxide group and other active group.Epoxy resin has a large amount of activity and polar group, as thermosetting resin, epoxy resin is widely used in the fields such as coating, composite coating, sizing agent, electronic package material, engineering plastics, civil construction material with its excellent over-all properties, good cohesiveness, excellent mechanical property, the manufacturability that cure shrinkage is little, good, excellent electrical insulation capability, corrosion resistance nature.
The application of epoxy resin widely, the consumption of annual epoxy resin is more than 1,000,000 tons, and the raw material preparing epoxy resin is mainly derived from oil, under the situation that current oil resource is day by day exhausted, the raw material production epoxy resin of originating in the urgent need to using other, reduces the dependence to petroleum resources.
Poly(lactic acid) (PLA) a kind ofly typically derives from the bio-renewables such as corn, potato and have the macromolecular material of excellent biological degradability.Meanwhile, poly(lactic acid), as the thermoplastic polymkeric substance of one, has good processibility and biocompatibility, be applicable to extrude, injection moulding, spinning, blown film, the multiple method processing such as two-way stretch, therefore, poly(lactic acid) has broad application prospects and development potentiality.
Chinese invention patent CN103435576A provides a kind of preparation method of oxysuccinic acid base epoxy, first under the existence of acid binding agent, obtain a kind of oxysuccinic acid diallyl ester by dehydrohalogenation by oxysuccinic acid and allylation reagent, then reacted by oxysuccinic acid diallyl ester and peralcohol and obtained.Chinese invention patent CN102796063A provides a kind of preparation method of novel monohydroxy bio-based epoxy resin, first utilizes cardanol glycidyl ether and unsaturated fatty acids or cardanol to react, and generates the unsaturated bio-based resin A of monohydroxy; Unsaturated double-bond on Resin A aliphatic chain is carried out the monohydroxy epoxy resin that epoxidation obtains a kind of high Bio-based content again.Chinese invention patent CN102250315A provides a kind of preparation method of amino-acid-derived epoxy resin, TYR cyclisation is prepared into the connection phenol of the six-ring containing aryl; Be that monomer prepares epoxy resin with single stage method with described phenol.Chinese invention patent CN102558507A provides a kind of preparation method giving birth to matter epoxy resin, first by xylogen, polyvalent alcohol, catalyzer and solvent Homogeneous phase mixing, add anhydride compound again and carry out esterification, be carboxylic acid group by the hydroxyl modification of xylogen, recycling multi-epoxy compounds carries out epoxidation modification, obtains raw matter epoxy resin.
Up to the present, yet there are no the document directly utilizing poly(lactic acid) synthetic epoxy resin and patent report in prior art.
Summary of the invention
For solving an above existing difficult problem, the invention discloses a kind of preparation method of bio-based epoxy resin, concrete scheme is as follows:
1, in low molecular weight, add maleic anhydride, controlling temperature of reaction is 100 ~ 140 DEG C, reacts 2 ~ 6h, obtain the poly(lactic acid) of two ends carboxy blocking under atmosphere of inert gases.
2, remove the stopper in glytidyl methacrylate and water, concrete technology is: glytidyl methacrylate is crossed post through 100 ~ 200 object neutral alumina columns; Add anhydrous magnesium sulfate vibration absorption trace water, filter, leave standstill 6 ~ 12h; Carry out underpressure distillation to filtrate, temperature is 70 ~ 150 DEG C, and vacuum tightness is 20 ~ 80mmHg, and uses agitator to stir, and distillation time is 2 ~ 6h.
3, glycidyl third fat of step 2 gained is added in the poly(lactic acid) of step (1) gained and the DMSO solution of zinc powder, the polydactyl acid that two ends are double bond is prepared under nitrogen protection and agitation condition, temperature of reaction is 60 ~ 100 DEG C, and the reaction times is 6 ~ 12h; The consumption of zinc powder is 0.1 ~ 0.5% of reactant total mass; The mass ratio of poly(lactic acid) and glytidyl methacrylate is 1: (0.04 ~ 2).
4, the reaction solution of step 3 gained is poured in a large amount of ethanolic solns, vigorous stirring, finally by throw out at room temperature drying under reduced pressure 24h, obtain the polydactyl acid that two ends are double bond.
5, be that the polydactyl acid of double bond adds in DMSO solvent and dissolves by the two ends of step 4 gained, then initiator and glytidyl methacrylate is added, start whipping appts simultaneously, temperature of reaction is 60 ~ 100 DEG C, reaction times is 3 ~ 8h, the consumption of initiator is 0.5 ~ 3%, and two ends are the polydactyl acid of double bond and the mol ratio of glytidyl methacrylate is 1: (15 ~ 90).
6, the methanol extraction adding 8 ~ 15 times amount in the reaction solution of step 5 gained goes out multipolymer, suction filtration repeatedly washing, finally dry 24h under vacuum.
7, under 25 ~ 100 DEG C of conditions, the solidifying agent that massfraction is 5 ~ 25% is added in the epoxy resin of step 6 gained, pre-dispersed 5 ~ 20 minutes, resin to be poured in mould and be incubated 2 ~ 6 hours at 60 ~ 100 DEG C, last at 110 ~ 160 DEG C after fixing 1 ~ 4 hour, obtain desired product.
Present invention process is simple, and poly(lactic acid) derives from corn, potatoes and other crops, and raw material sources are extensive, and is conducive to reducing macromolecular material to the consumption of petroleum resources and reduction CO
2discharge, gained epoxy resin has lower viscosity, good cementability, can be used as the matrix of tackiness agent, coating and matrix material, is applicable to the moulding process of multiple matrix material.Therefore, this invention has comparatively wide application prospect.
Embodiment
By following examples, the present invention is described, but does not limit the present invention.
Embodiment 1
1, in the there-necked flask of 100ml, add 20gPLA (it is 8800 that number has divided equally amount), 0.3g maleic anhydride, controlling temperature of reaction is 120 DEG C, at N
24h is reacted under atmosphere.
2,2g glytidyl methacrylate is crossed post through 200 object neutral alumina columns, then add 0.5g anhydrous magnesium sulfate vibration absorption trace water, filter, leave standstill 10h; 80 DEG C, vacuum tightness is that 50mmHg carries out underpressure distillation to filtrate under condition, and uses agitator to stir, distillation time is 4h.
3, in 100ml there-necked flask, add the product of step 1 gained, 1.8g glytidyl methacrylate and 62.4mg zinc powder and 50mlDMSO make solvent, in nitrogen protection atmosphere, in 80 DEG C of isothermal reaction 10h under magnetic agitation effect.
4, after reaction terminates, reaction solution is poured in 70ml ethanolic soln, and high degree of agitation, be settled out product, remove unreacted monomer simultaneously, finally by product at room temperature drying under reduced pressure 24h.
5, in 100ml there-necked flask, add the product of 60mlDMSO and step 4 gained, add the AIBN of 16.36g glytidyl methacrylate and 2% after thoroughly dissolving, then start to stir, and pass into N2 protection, temperature of reaction is 70 DEG C, and the reaction times is 8h.
6, the methanol extraction adding 10 times amount in the reaction solution of step 5 gained goes out multipolymer, and suction filtration also washs 3 times, finally dry 24h under vacuum.
7, at 60 DEG C, in the epoxy resin of step 6 gained, add the mphenylenediamine that massfraction is 18%, pre-dispersed 10 minutes, resin to be poured in mould and be incubated 3 hours at 80 DEG C, finally after fixing 2 hours at 120 DEG C.
Embodiment 2
1, in the there-necked flask of 100ml, add 20gPLA (it is 8800 that number has divided equally amount), 0.28g maleic anhydride, controlling temperature of reaction is 130 DEG C, at N
23h is reacted under atmosphere.
2,2g glytidyl methacrylate is crossed post through 200 object neutral alumina columns, then add 0.5g anhydrous magnesium sulfate vibration absorption trace water, filter, leave standstill 8h; 80 DEG C, vacuum tightness carries out underpressure distillation to filtrate under being the condition of 60mmHg, and uses agitator to stir, distillation time is 4h.
3, in 100ml there-necked flask, add the product of step 1 gained, 1.6g glytidyl methacrylate and 62.4mg zinc powder and 50mlDMSO make solvent, in nitrogen protection atmosphere, in 80 DEG C of isothermal reaction 10h under magnetic agitation effect.
4, after reaction terminates, reaction solution is poured in 70ml ethanolic soln, and high degree of agitation, be settled out product, remove unreacted monomer simultaneously, finally by product at room temperature drying under reduced pressure 24h.
5, in 100ml there-necked flask, add the product of 60mlDMSO and step 4 gained, after thoroughly dissolving, add the BPO of 10g glytidyl methacrylate and 3%, then start to stir, and pass into N
2protection, temperature of reaction is 60 DEG C, and the reaction times is 10h.
6, the methanol extraction adding 12 times amount in the reaction solution of step 5 gained goes out multipolymer, and suction filtration also washs 3 times, finally dry 24h under vacuum.
7, at 60 DEG C, in the epoxy resin of step 6 gained, add the triethylene tetramine that massfraction is 13%, pre-dispersed 15 minutes, resin to be poured in mould and be incubated 2 hours at 80 DEG C, finally after fixing 2 hours at 120 DEG C.
Claims (7)
1. a preparation method for bio-based epoxy resin, is characterized in that, described low molecular weight and maleic anhydride temperature of reaction are 100 ~ 140 DEG C, under atmosphere of inert gases, react 2 ~ 6h.
2. a preparation method for bio-based epoxy resin, is characterized in that, the stopper in removing glytidyl methacrylate and water, and concrete technology is: glytidyl methacrylate is crossed post through 100 ~ 200 object neutral alumina columns; Add anhydrous magnesium sulfate vibration absorption trace water, filter, leave standstill 6 ~ 12h; Carry out underpressure distillation to filtrate, temperature is 70 ~ 150 DEG C, and vacuum tightness is 20 ~ 80mmHg, and uses agitator to stir, and distillation time is 2 ~ 6h.
3. the preparation method of a bio-based epoxy resin, it is characterized in that, preparation two ends are the polydactyl acid technique of double bond is glytidyl methacrylate added in the DMSO solution of poly(lactic acid) and zinc powder, under nitrogen protection and agitation condition, controlling temperature of reaction is 60 ~ 100 DEG C, and the reaction times is 6 ~ 12h; The consumption of zinc powder is 0.1 ~ 0.5% of reactant total mass; The mass ratio of poly(lactic acid) and glytidyl methacrylate is 1: (0.04 ~ 2).
4. the preparation method of a bio-based epoxy resin, it is characterized in that, washing and purification two ends are the method for the polydactyl acid of double bond is that the reaction solution being the polydactyl acid of double bond by preparation two ends is poured in a large amount of ethanolic solns, vigorous stirring, finally by throw out at room temperature drying under reduced pressure 24h.
5. the preparation method of a bio-based epoxy resin, it is characterized in that, two ends are the polydactyl acid of double bond and glytidyl methacrylate reaction conditions under initiator effect, solvent adopts DMSO, continuous stirring, temperature of reaction is 60 ~ 100 DEG C, and the reaction times is 3 ~ 8h, the consumption of initiator is 0.5 ~ 3%, and two ends are the polydactyl acid of double bond and the mol ratio of glytidyl methacrylate is 1: (15 ~ 90).
6. the preparation method of a bio-based epoxy resin, it is characterized in that, described epoxy resin post-treating method is, the methanol extraction adding 8 ~ 15 times amount in two ends are the polydactyl acid of double bond and glytidyl methacrylate reaction solution goes out multipolymer, suction filtration repeatedly washing, finally dry 24h under vacuum.
7. the preparation method of a bio-based epoxy resin, it is characterized in that, the preparation method of described solidifying product is, under 25 ~ 100 DEG C of conditions, the solidifying agent that massfraction is 5 ~ 25% is added in gained epoxy resin, pre-dispersed 5 ~ 20 minutes, resin to be poured in mould and be incubated 2 ~ 6 hours at 60 ~ 100 DEG C, finally after fixing 1 ~ 4 hour at 110 ~ 160 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410353485.2A CN105273166B (en) | 2014-07-24 | 2014-07-24 | A kind of preparation method of biological base epoxy |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410353485.2A CN105273166B (en) | 2014-07-24 | 2014-07-24 | A kind of preparation method of biological base epoxy |
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| Publication Number | Publication Date |
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| CN105273166A true CN105273166A (en) | 2016-01-27 |
| CN105273166B CN105273166B (en) | 2017-10-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474233A (en) * | 2017-08-20 | 2017-12-15 | 芜湖通全科技有限公司 | A kind of preparation method of PLA base epoxy |
| CN109384775A (en) * | 2018-08-29 | 2019-02-26 | 中国科学院宁波材料技术与工程研究所 | A kind of biological base epoxy presoma and its preparation method and application containing cyclic amide structure |
| CN109384748A (en) * | 2018-08-24 | 2019-02-26 | 中国科学院宁波材料技术与工程研究所 | Biological base epoxy based on natural amino acid and its preparation method and application |
| CN117701112A (en) * | 2024-01-23 | 2024-03-15 | 中建国际工程有限公司 | Water-based building anti-corrosion coating and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474233A (en) * | 2017-08-20 | 2017-12-15 | 芜湖通全科技有限公司 | A kind of preparation method of PLA base epoxy |
| CN109384748A (en) * | 2018-08-24 | 2019-02-26 | 中国科学院宁波材料技术与工程研究所 | Biological base epoxy based on natural amino acid and its preparation method and application |
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| CN117701112A (en) * | 2024-01-23 | 2024-03-15 | 中建国际工程有限公司 | Water-based building anti-corrosion coating and preparation method thereof |
| CN117701112B (en) * | 2024-01-23 | 2024-05-07 | 中建国际工程有限公司 | Water-based building anti-corrosion coating and preparation method thereof |
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